Aromatic sulphonation. Part 92. Sulphonation of the three methylphenols and the six dimethylphenols in concentrated aqueous sulphuric acid; and the lsomerization of some of the resulting sulphonic acids and of m-xylene-2-and o-xylene-3-sulphonic acid

Abstract

The isomer distributions for the mono- and di-sulphonation of the three methylphenols in 81.6–90.0% sulphuric acid and of the six dimethylphenols in 84.9% sulphuric acid at 35 °C have been determined by means of 1H n.m.r. spectroscopy. Products that would result from demethylation, disproportionation, or ipso-substitution have not been observed. The monosulphonation isomer distribution of each of the three methylphenols is independent of the sulphuric acid concentration. 2,4-Dimethylphenol in 84.9% H2SO4yields 19% 5- and 79% 6-sulphonic acid, and 2,6-dimethylphenol yields 28% 3- and 72% 4-sulphonic acid. With the phenols (2), (3), (5), and (7), which have positions both ortho and para to the –OH substituent available for sulphodeprotonation, the yield of ortho-substitution is relatively high, viz. 44, 45,36, and 27%, respectively. The mono- and di-sulphonic acids of which the sulpho group is between the –OH and an –Me group are unstable under the reaction conditions employed, with the exception of the 3,5-dimethylphenol-2-sulphonic acid. It is proposed that their isomerization proceeds by protiodesulphonation followed by resulphonation to yield the more stable sulphonic acid isomer(s). From a kinetic analysis of the calculated first-order rate coefficients for protiodesulphonation, it is concluded that the unprotonated substrate species is the entity undergoing the protiodesulphonation.